Positive electrode materials for lithium batteries based on VOPO4

A detailed electrochemical study of Li insertion in the -form of VOPO₄ and the optimization of the cycling performance are presented. The redox process occurs in one step close to 3.76 V, along with a phase transition. In order to improve the intercalation kinetics, the electronic conductivity was optimized by introducing a mixed valency, and the ionic conductivity was favored by introducing ‘pillaring’ molecules or ions in the interlayer space. In this way, the electrochemical behaviors of -VOPO₄·2H₂O, -Na_xVOPO₄, -K_xVOPO₄ and -Mg_xVOPO₄ (0≤x≤1) have been studied: the hydrate compound shows a good specific capacity (100 mA h/g at a C/5 regime), but a poor cyclability was mainly because of water oxidation. The inserted large alkaline ions improved the cyclability up to 80 cycles (Na⁺) or over 100 cycles (K⁺). Enhancements of the VOPO₄ specific capacity have been obtained as well by mechanical ball-millings.     

Homogenization of elastic–viscoplastic heterogeneous materials: Self-consistent and Mori-Tanaka schemes

This paper deals with the prediction of the macroscopic behavior of a multiphase elastic–viscoplastic material. The proposed homogenization schemes are based on an interaction law postulated by Molinari et al. [Molinari, A., Ahzi, S., Kouddane, R. 1997. On the self-consistent modelling of elastic–plastic behavior of polycrystals. Mech. Mater., 26, 43–62]. Self-consistent schemes are developed to describe the behavior of disordered aggregates. The Mori-Tanaka approach is used to capture the behavior of composite materials, where one phase can be clearly identified as the matrix. The proposed schemes are developed within a general framework where compressible elasticity and anisotropy of the materials are taken into account. Inclusions can have various shapes and orientations. Illustrations of the homogenization procedure are given for a two-phase composite materials. Comparisons between results of the literature and predictions based on the interaction law are performed and have demonstrated the efficiency of the proposed homogenization schemes.     

Photoresponsive polyamides containing pentamethylated norbornadiene moieties: Synthesis and photochemical properties under sunlight irradiation

Photoresponsive polyamides containing main‐chain pentamethylated norbornadiene (NBD) moieties are obtained in quantitative yields via the Yamazaki–Higashi reaction between a pentamethylated NBD dicarboxylic acid and a series of aromatic diamines. Chemical structures are confirmed by ¹H and ¹³C NMR and weight average molar masses measured by SEC are in the range of 21,500–28,600 g mol^?1 with chain dispersities close to 2. Physical properties are investigated by FTIR, differential scanning calorimetry (DSC), thermogravimetric analysis, and viscosimetry. All obtained polyamides are amorphous with glass transition temperatures ranging from 68 to 124 °C. They are soluble at room temperature in common organic solvents and exhibit good thermal stabilities with T_d10 values ranging from 175 to 276 °C. The photochemical isomerization of the NBD moiety into quadricyclane (QC) is studied by UV/vis spectroscopy after sunlight irradiation of polymer films. For all polyamides, a first‐order kinetic rate is observed for the conversion of NBD to QC. The thermal release of the stored energy associated to the reverse transformation of QC groups into NBD ones is about 90–95 kJ mol^?1 as measured by DSC of the irradiated polymer films. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4650–4656     

Runup and green water velocities due to breaking wave impinging and overtopping

The present study investigates, through measurements in a 2D wave tank, the velocity fields of a plunging breaking wave impinging on a structure. As the wave breaks and overtops the structure, so-called green water is generated. The flow becomes multi-phased and chaotic as a large aerated region is formed in the flow in the vicinity of the structure while water runs up onto the structure. In this study, particle image velocimetry (PIV) and its derivative, bubble image velocimetry (BIV), were employed to measure the velocity field in front and on top of the structure. Mean and turbulence properties were obtained through ensemble averaging repeated tests. The dominant and maximum velocity of the breaking wave and associated green water are discussed for the three distinct phases of the impingement–runup–overtopping sequence. Initially the flow is mainly horizontal right before the breaking wave impinges on the structure. The flow then becomes primarily vertical and rushes upward along the front wall of the structure right after the impingement. Subsequently, the flow becomes mainly horizontal on top of the structure as the remaining momentum in the wave crest carries the green water through. The distribution of the green water velocity along the top of the structure has a nonlinear profile and the maximum velocity occurs near the front of the fast moving water. Using the measured data and applying dimensional analysis, a similarity profile for the green water flow on top of the structure was obtained, and a prediction equation was formulated. The prediction equation may be used to predict the green water velocity caused by extreme waves in a hurricane.     

Dihydrogen activation with (t)Bu3P/B(C6F5)3: a chemically competent indirect mechanism via in situ-generated p-(t)Bu2P-C6F4-B(C6F5)2

A chemically competent indirect pathway for the activation of dihydrogen by the nonmetal Lewis acid/Lewis base pair (t)Bu(3)P/B(C(6)F(5))(3) is described. The reaction between (t)Bu(3)P and B(C(6)F(5))(3) produces [(t)Bu(3)PH](+)[FB(C(6)F(5))(3)](-) and the known phosphinoborane p-(t)Bu(2)P-C(6)F(4)-B(C(6)F(5))(2) (1-(t)Bu) with elimination of isobutylene. At 1:1 stoichiometry, 1-(t)Bu is produced rapidly in detectable quantities and can act as a catalyst for the formation of [(t)Bu(3)PH](+)[HB(C(6)F(5))(3)](-) from (t)Bu(3)P and B(C(6)F(5))(3) in the presence of H(2). The extent to which this indirect path competes with the direct path is explored.     

Exploring the Chemistry of the P-Complexed Parent Phosphine

Abstract

Whereas the parent phosphine is a highly poisonous, easily oxidized gas, a phosphine complex such as W(CO)₅PH₃ is much easier to handle, as this complex is an air stable white solid.     

5,5‐Dimethyl‐2,8‐diphenyl‐5H‐dibenzo[b,f]silepine: a synchrotron study

The molecule of the title silepine compound, C₂₈H₂₄Si, lies on a crystallographic general position but has almost exact mirror symmetry. The seven‐membered silepine ring has a boat conformation, with a fold angle of 99.99 (9)° between the C—C=C—C stern and the C—Si—C prow. The planes of the phenyl substituents are rotated by 32.23 (6) and 31.80 (7)° out of the planes of the respective fused benzene rings. Similar folded conformations are found for other dibenzo[b,f]silepines, while analogous dibenzo[b,f]borepines, in which the B atom can participate in conjugation, have a more flattened heterocyclic ring.     

Large spontaneous polarization and clear hysteresis loop of a room-temperature hybrid ferroelectric based on mixed-halide [BiI3Cl2] polar chains and methylviologen dication

The search for hybrid organic-inorganic materials, which have the great advantage that they can be synthesized at moderate temperature (T < 200 °C), remains a great challenge in the field of ferroelectrics. Here, a room-temperature ferroelectric material with interesting characteristics, (MV)[BiI(3)Cl(2)] (MV(2+) = methylviologen), is reported. Its structure is based on polar inorganic chains resulting from a remarkable Cl/I segregation induced by methylviologen entities, which coincide with the fourfold polar axis of the tetragonal structure. Of great importance is that this room-temperature hybrid ferroelectric displays a clear electrical hysteresis loop with a large spontaneous polarization (>15 μC·cm(-2)).     

Optical preprocessing for texture classification using specialized binary black and white pseudocoloring masks

Image texture is a neighborhood information which is time consuming to analyze by computer. Optical processing can be used as a preprocessor to reveal some of the texture information in parallel on the whole image before classification of the preprocessed image by computer. Pseudocoloring allows an easy discrimination of texture information. A specialized binary black and white mask is introduced which selects at one particular wavelength one peak of the diffracted power spectrum of each texture considered. The method is applicable to textures showing some periodicity. The resolution, selectivity and difficulties of the method are described qualitatively and an experimental example including a problem of partial cross talk between different textures is presented.